Composition of 4, 4-bis(hydroxyaryl) pentanoic acid co-esters and polyepoxides



COMPOSITION OF 4,4-BIS(HYDROXYARYL) PEN- TANOIC ACID CO-ESTERS AND POLYEPOXIDES Sylvan O. Greenlee, Racine, Wis., assignor to S. C. Johnson & Son, Inc., Racine, Wis.

N Drawing. ApplicationNovember 7, 1956 Serial No. 620,812

Claims. (Cl. 260-18) This invention relates to new products and compositions resulting from the reaction of polyepoxides with mixed esters prepared from hydroxyaryl-substituted aliphatic acids, modifying organic acids, and polyhydric alcohols, the compositions being valuable in the manufacture of varnishes, molding compositions, adhesives, films, molded articles, etc. According to the present invention, the polyepoxide materials and mixed esters may be reacted in regulated proportions to produceinitial re action mixtures as well as intermediate and final reaction products.

An object of this invention is the production of compositions containing polyepoxides and mixed esters of hydroxyaryl-substituted aliphatic acids, modifying organic acids, and polyhydric alcohols in proportions suitable for reaction to form resins, films, coating compostions, etc.

Another object of this invention is the production of intermediate reaction products from initial reaction mixtures of these polyepoxides and mixed esters capable of further reaction on the application of heat to form insoluble, infusible products.

Another object of this invention is the production of initial and intermediate reaction mixtures of the hereinbefore described character which are stable at ordinary temperatures for relatively long periods of time yet which may be converted to polymeric products upon the application of heat.

Still another object of this invention is the production of final reaction products from these initial and intermediate reaction mixtures characterized by such physical properties as hardness, flexibility, and toughness, and such chemical properties'as resistance to the ordinary chemicals and water. These and other objects and advantages are attained by the present invention, various novel features of which will become more fully apparent from the following description with particular reference to specific examples which are to be considered as illustrative only.

In general, the polymeric reaction products of this invention are obtained by reacting the epoxide groups of polyepoxides with the active hydrogen-containing groups of mixed esters prepared from polyhydric alcohols, modifying organic acids, and hydroxyaryl-substituted aliphatic acids. Epoxide groups, it is known, will react with active hydrogen-containing groups, that is, groups containing hydrogens attached to oxygen, nitrogen, or sulfur, with the formation of hydroxyl groups and a linking of the oxygen, nitrogen, or sulfur atoms to the split epoxide residues. In the case of hydroxyl groups, the splitting of the epoxide groups is accompanied by the formation of ether linkages. The mixed esters employed in this invention, which are prepared to contain free hydroxyl groups, interreact with the polyepoxides to form polymeric products containing ether linkages formed by the reaction of epoxide groups. The products have remarkable characteristics such as toughness, flexibility, and chemical resistance.

A number of varied and desirable properties can be imparted to the reaction mixtures and products derived therefrom by proper selection of the mixed ester employed in the reaction mixtures. In the preparation of a polymeric resin composition, for example, one of the problems encountered is the manner of plasticizing the composition, or the manner of imparting air-drying or heat-converting characteristics to the composition, without sacrificing other desirable properties. According to the present invention, the plasticity or conversion characteristics can readily be adjusted by proper selection of the modifying organic acid used in the mixed ester. Further variations can be obtained through the selection of the polyhydn'c alcohol employed in preparting the mixed ester.

The mixed esters generally are conveniently prepared by esterifying polyhydric alcohols with the hydroxyarylsubstituted aliphatic acids and modifying organic acids under conditions whereby the aryl-hydroxyl groups of the hydroxyaryl-substituted aliphatic acids are substantially unreacted. Since these aryl-hydroxyl groups are more acidic in nature than the alcoholic hydroxyl groups of the polyhydric alcohols, the reaction of aryl-hydroxyl groups will be insignificant in those cases where the reaction mixtures contain about equivalent amounts or more of alcoholic hydroxyl groups for each equivalent of carboxyl groups, and generally it was found that excellent products were obtained using such proportions.

The hydroxyaryl-substituted alkylidene carboxylic acid contemplated for use herein should have two hydroxyaryl groups attached to a single carbon atom. The preparation of such an aryloxy acid is most conveniently carried out by condensing a keto-acid with the desired phenol. Experience in the preparation of bisphenol and related compounds indicates that the carbonyl group of the keto-acid should be positioned next to a terminal methyl group in order to obtain satisfactory yields. Prior applications, Serial Nos. 464,607 and 489,300, filed October 25, 1954, and February 18, 1955, respectively, disclose a number of illustrative compounds suitable for use as the Diphenolic Acid and methods of preparing the same. These materials, which are referred to for convenience as Diphenolic Acid or DPA, consist of the condensation products of levulinic acid and phenol, substituted phenols, or mixtures thereof. It is to be understood that the phenolic nuclei of the Diphenolic Acid may be substituted with any groups which will not interfere with the reactions contemplated herein. For example, the nuclei may. be alkylated with alkyl groups of from 1-5 carbon atoms as disclosed in my copending application Serial No. 489,300 or they may be halogenated. The Diphenolic Acid derived from substituted phenols, such as the alkylated phenols, are sometimes more desirable than the products obtained from unsubstituted phenols since the alkyl groups provide better organic solvent solubility, flexibility, and water resistance. However, the unsubstituted product is usually more readily purified. 1

Polyhydric alcohols which may be used in the preparation of the mixed esters include both the resinous and nonresinous-type alcohols. Illustrative of the nonresinous 3 glycol, polyethylene glycols, propylene glycol, polypropylene glycols, 1,4'-butanedio l, 2,5-pentanediol, 1,6- hexanediol, neopentyl glycol, glycerol, erythritol, pentaery-thritol, polypentaerythritols, sorbitol, mannitol, alphamethyl glucoside, polyallyl alcohols, diethanolamine, tnethanolarnine and tetramethylol cyclohexanol.

The resinous polyhydric alcohols which may be employed can be illustrated by such \products as those prepared by the reaction of phenol-formaldehyde condensa e w th-. hl qh rl i For ex mp ana kyl ph m be condensed'withformaldehyde toform an intermediatemethanolderivative andan alkaline solution of this intermediate may then be treated with a chlorohydrin, such as glycerol monochlorohydrin, to yield after conidensationffa polymeric polyhydric alcohol. Still other smous polyhydric alcohols maybe illustrated by the alcoholic epoxide resins which are ,polyether derivatives of polyhydric phenols and such polyfu nctional ,materials :as polyhalohydrins, polyepoxides," or epihalohydrins. Reaction products .ma'y be prepared which are monomeric or polymeric polyhydric alcohols having aliphatic "and aromatic nuclei connected to each'otherby ether linkagesand containing terminal epoxide' groups. Prep- ;ar-ationsof these epoxide. materials, asfwell as some illus- Ztrative exampleslaredescribed in UlS. Patents 2,456,408, 2,503,726, 2,615,007, 2,615,008, 2,668,805, 2,668,807, ,and 2,698,315. Welhknown commercial .examplespf these resins are the Epon resins marketed by the Shell -Chemical Corporation which have molecular weights of w abou 8,000 r The modifying organic acids employed with the hydroxyaryl substituted aliphatic acids in preparing the fmixedesters used inithis invention, includea wide variety ,of aliphatic .or aromatic, resinous or nonresinon's, short- .or-long-chain, saturatedor unsaturated materials. The selection of the'material depends on the characteristics thatit is desired to ta the Lfinal polymeric products of invention.

Selfrplasticized compositions, which in addition have .air dry ing characteristics, may be prepared by employing as the modifying organic acid the drying oil fatty acids, these acids normally contain from about 18 to 22 carbon atoms and are obtained by thesaponification ofinaturally .h h i s r e i tah wih- Othe v cids m y b illustrated by thelish oil :acids and theshorter chained saturatedacid, undecanoic acid which is a decomposiii? product T f a lP Q l a id M x e te pr pare thesematerials suitable for use in this invention are vrr'lore lfully described ina copending application of Greenl ee, ;1'iled'1April 11, 1 95 5, having Serial No. 500,695, ,entitled flylixedfisters. Low molecular weight unsat urated @aPiQ JI1W1 P9 E P if 9 1 3 a r-do o h -c m ,i g 9haracteristicsare desired-sincetheplasticizationeffect of. the'low molecular weight materials is insignificant. of such acids are crotonic acid and sorbic aci The saturatcd rnonobasic aliphatic acids may also ,be .ltSfld in the production of the mixed esters. vSuch acids ,Qfih a Q E YQPl P man o e ating th pl i y of 1I h ih hmd qt Exam le of h s a sa a e ,decanoicand stearic acid. In general the longer .chain 32;.h? Y l g;.- Q hfil fib u 9 arbon atomirarelthc 9 @139 P fi iPi F Thhlq l fiha satu ated aci may ,be obtained by saponification of the vegetable and fish oil acids, thelunsatur ated acids being first hydrogenated to remove their uns'aturation. longer chain saturated acids maybe obtained by the saponification of naturally occurring waxes or by chemicalfsynthes'is using @the so-oalled- Oxo process. I V I Mixed esters prepared from resinous acids are advantageously employed in some inst ances. For example,

rosinacids. are .generally usedin the preparation of poly- Jng lclprqductssto impart hardness, gloss, and other resiall l C,tcristic s.I..Mixed esters prepared .from such fll 4 a al IQ ac d may be advantageousl employed in this invention. The preparation of such mixed esters is more fully described in the copending application of Greenlee entitled Mixed Resin Acid Esters, Serial No. 519,279, filed June 30, 1955. Aromatic acids also are valuable as the modifying organic acid and may be illustrated by such materials as benzoic acid, butyl benzoic acid, phthalic acid, naphthoic acid, and phenoxy acetic acids. These acids are useful in imparting hardness, rigidity, and toughness to the polymeric products derived therefrom. The modifying acids used in the preparation of the mixed esters also include the dibasic acids such as succinic acid, azelaic acid, sebacic acid, and longer chain acids such as the 36 carbon acids prepared by .dimerizing unsaturated, vegetable oil acids. In the ,preparation .of .the ,mixed esters .from .polyhydric alcohols, .hydroxyaryl-substituted acids and modifying organic acids, the reactants may be used in varyingp'roporti'ons of wide ranges.

The-ratio of acid to polyhydn'c alcoholmaylbe adjusted so that substantially equivalent amounts of carboxyl and hydroxyl groups are present in the mixture. Such compositions have been found to: be particularly valuable. However, it has been found that the hydroxyl content of the mixture can beincreased greatlyso as tobe substantially inexcess of carboxyl groups, for example in the range of about 5: 1, and valuable products are obtained. However, in thismixture since relatively smallarnounts of acid are. present their effect in the final polymeric product tendstotbe diminished.

Similarly, the ratio of hydroxyaryl-substituted acid .to the modifying organic acid maybe proportioned within relatively large ranges. Remarkable productswere 0btained, for examplewhen the ratio of hydroxyaryl-substituted acid to modifying organic acid ranged from about 1:5 and 5:1. The particular ratio employed,of course, would depend upon the choice of acids used and the modifications desired in the reaction mixtures and polymericmaterials preparedfrom the mixedesters.

The mixed esters of this invention are conveniently prepared by direct heating ,attemperatures of from 275 C. with provision for the continuous removal of Water produced by the condensation. Since the, Diphenolic Acid and many of the other organic acids, as Well as the polyhydric alcohols, .have relatively high .boiling points, which are in most cases above 190 0.,

water. can be removed by permitting it to volatilize during esterification. In the case of thepreparation of the .estersof more volatile organic acids, it is convenient to use the anhydridesor sometimes the acid chlorides. .For

example, the preparation of a mixed ester containing the acetate would conveniently be prepared .byusing acetic anhydride for the esterification. ,In the preparationof the higher esters where high temperature .is used, removal. ofth water maybe facilitated by continuously bubbling through the reaction mixture during esterification a istream ofinen gas, such as carbon dioxide or removed by az eotropic distillation, permitting thesolvent e w h ih thh Wa a r The .Q dh 9f dd h of th va i u in red e t rD phenolic Acid, other organic acids, and polyhydric alcoh91S,;-l 0j each other may bevaried. It is sqm etimes advantageous to vary the order of reaction'to obtain to return to the reaction mixture after havingdropp ed prt hshmy c l l w a P tic om in i n o ,gred nts used. In the art of high temperature .este rifi- .Q tion is somet m esirab e to use c ta es hr ca ion, ata y ts, a t e e may h v us in. the-p p ration of the .s biect .mixed esters. Anothervariation; in the. methodpf preparing themixed. esters .isthat. of

the utilization of azeotropic distillation with a small amount of xylene, the xylene being sufiicient to give refluxing at the temperature of esterification. The proportions given are expressed as parts by weight unless otherwise indicated. Acid value represents the number of milligrams of KOH required to neutralize a l-gram sample and were determined by direct titration. Softening points were determined by Durrans Mercury Method (Journal of Oil and Color Chemists Association, 12, 173-175 [1929]).

EXAMPLE I A mixture of 143 parts of 4,4bis(4-hydroxyphenyl)- pentanoic acid and 70 parts of soyabean oil fatty acids was heated to 230 C. at which point 38 parts of dipentaerythritol were added over a period of 10 minutes. The reaction mixture was held at 230-240 C. for a period of hours, during the last 15 minutes of which time the pressure was reduced to about 20 millimeters. The resulting product amounting to 227 parts had an acid value of 2.8 and a softening point of 80 C.

EXAMPLE II A mixture of 51 parts of glycerol, 140 parts of dehydrated castor oil acids and 286 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid was heated over a period of 30 minutes to 90 C. and to 240 C. over a period of another hour. The reaction mixture was held at 240- 245 C. for a period of 4 /2 hours. The resulting product amounting to 448 parts had an acid value of 9.5 and a softening point of 65 C.

EXAMPLE III A mixture of 278 parts of Epon resin 1004 and 224 parts of linseed oil acids was heated at 220224 C. for a period of 1 /2 hours. To this mixture was added 57.2 parts of 4,4-bis(4-hydroxyphenyl)pentanoic acid and the heating continued at 230-240 C. for an additional 2% hours. The resulting product had an acid value of 7 and a softening point of'63 C.

EXAMPLE IV A mixture of 280 parts of dehydrated castor oil acids and 149 parts of pentaerythritol was heated to 235 C. and held at this temperature for a period of 1 /2 hours, at which point 797 parts of 4,4-bis(4-hydroxyphenyl)- pentanoic acid was added and the heating continued at 210 C. for 6 /2 hours. The reaction mixture was finally heated to 240 C. over a period of /2- hour during which time the pressure was reduced to 20 millimeters. The resulting product amounted to 1130 parts and had an acid value of 7.6 and a softening point of 69 C.

EXAMPLE V A mixture of 172 parts of 4,4-bis (4-hydroxypheny1) pentanoic acid and 56 parts of linseed oil acids was heated to 220 C. at which point 30 parts of pentaerythritol were added slowly over a period of 12 minutes and the reaction continued at 215225 C. for a period of 6 hours. The pressure was reduced to around 20 millimeters during the latter 18 minutes of the reaction period. The product amounting to 232 parts had an acid value of 5 and a softening point of 79 C.

EXAMPLE VI A mixture of 280 parts of chinawood oil acids and 150 parts of pentaerythritol was heated at 225 C. until the acid value had reached 6. To this mixture was added ,850 parts of 4,4-bis(4-hydroxphenyl)pentanoic acid and the reaction mixture heated for a period of 2 hours at 210220 C. The pressure was reduced to 30 millimeters during the last20 minutes of heating. The resulting product had a softening point of C.

EXAMPLE VII A mixture of 343 partsof 4,4-bis(4-hydroxyphenyl)- pentanoic acid, 227 parts of stearic acid and 68 parts of glycerol was heated for a period of 1 hour at 203220 C. and for a period of 4 hours at 220-248i C. to give a product having an acid value of 2.9.

EXAMPLE VIII A mixture of 286 parts of 4,4-bis(4-hydroxyphenyl) pentanoic acid, 280 parts of soyabean oil acids and 68 parts of ethylene glycol was heated for a period of 40 minutes at 225 C. and for an additional period of 5 hours at 225-238 C. to give a product having an acid value of 9.5. 1

EXAMPLE IX A mixture of 286 parts of 4,4bis(4-hydroxyphenyl)- pentanoic acid, 280 parts of chinawood oil acids and 68 parts of ethylene glycol was heated for a period of 6 hours at 220-237 C. to give a product having an acid value of 2.9.

Illustrative of the epoxide compositions which may be employed in this invention are the complex epoxide resins which are polyether derivatives of polyhydric phenols with such polyfunctional coupling agents as polyhalohydrins, polyepoxides, or epihalohydrins. These compositions may be described as polymeric polyhydric alcohols having alternating aliphatic chains and nuclei connected to each other by ether linkages, containing terminal epoxide groups and free from functional groups other than epoxide and hydroxyl groups. It should be understood that significant amounts of the monomeric reaction products are often present. This would be illustrated by I to III below where n equals Zero. Preparation of these epoxide materials as well as illustrative examples are described in US. Patents 2,456,408, 2,503,726, 2,615,007, 2,615,008, 2,668,807, 2,688,805, and 2,698,315. Wellknown commercial examples of these resins are the Epon resins marketed by the Shell Chemical Corporation. Illustrative of the'preparation of these epoxide resins are the following reactions wherein the difunctional coupling agent is used in varying molar excessive amounts:

Polyhydric phenol and an epihalohydrin bis(hydroxyphenyl)isopropylidene excess epichlorohydriu Tl CE; CHr I O OHEHOHOHCHHO.

OCHICHOHCHOHOHZ oomononoriom Polyhydrle phenol and a polyhalohydrin bis(hydroxyphenyl) isopropylldene excess alpha-glyceroldichlorohydrin q c rnonom o oomononoaJ-o oornonon aqueous alkali Cfig \CH3 n CH3 CH3 III epoxide groups and alcoholic hydroxyl groups attached to the aliphatic portions of the resin, the latter being I formed by the splitting of 'epoxide groups in the reaction of the same with phenolic hydroxyl groups. Ultimately, the reaction with the phenolic hydroxyl groups 'ofthe polyhydric phenols is generally accomplished by means of'epoxide groups formed from halohydrins by the loss of hydrogen and halogenas shown by the following equations:

Other .epoxide compositions which may be used include the polyepoxide polyesters which maybe prepared by esterifying tetrahydrophthalic anhydride with a glycol and epoxidizing'the product of the esterification 'reeaction. In the preparation of the polyesters, tetrahydr'ophthalic acid may, also be used as well as the simple esters of tetrahydrophthalic acid such as dimethyl'and diethyl esters. There is a tendency with' tertiary glycol's' for dehydration to occur under the conditions usedfor. esterific'ation ;so that generally the primary and secondary glyeols are the most satisfactory in the polyester formation. Glycols'which may be used-in the preparation of this polyester composition comprise, in general, those glycols having. 2 hydroxyl groups attached 'to separate carbon: atoms and free ,from functional groups .Which would interfere with the .esterification or epoxidation reactions. These glycols include such glycols as ethylene gIycQIQdiethyIene glycol, triethylene glycol, tetramethylene glycol, propyleneglycol, polyethyle'neglycol, 'neopentyl .glycol, and hexamethylene, glycol. Polyepoxide polyesters may be prepared from these polyesters by epoxidizing the unsaturated portions of the tetr'ahydrophthalic acid residues in the polyester composition. By properly proportioning reactants in the polyester formation and regulating the epoxidation reaction, polyepoxides having up to 12 or more epoxide groups per molecule may be readily prepared. These polyepoxide polyester compositions as Well as their preparation are more fully described in a 'copending application having Serial No. 503,323,fild:APi1 2 2, 195s.

Polyepoxide compositions useful in this invention also include the epoxidiz ed unsaturated natural oil acidesters, including the unsaturated vegetable, animal, and fish oil acid esters made by reacting these materials with various oxidizing agents. Those unsaturated oil acid esters are long chain aliphatic acid 'esters containing from about 15 to 22 carbon atoms I These acids may beesterified by simple monohydric alcohols such as methyl, ethyl, or decyl alcohol, by polyhydric alcohols such asglycerol, pentaerythritol, polyallyl alcohol, or resinous polyhydric alcohols. Also suitable are the mixed esters of polycarboxylic acids and long chain unsaturated natural oil acids Withpolyhydric alcohols, such as glycerol and pentaerythritol. These epoxidized oil acid esters may contain more than 1 up to 20 epoxide groups per molecule. The method of epoxidizing these unsaturatedoil acidesters consists oftr eating them with various oxidizing agents, such as the organic peroxides and the peroxy acids, or with one of the various forms of hydrogen peroxide. Ajtypical procedure practiced in the art'consists'of using hydrogen peroxide in the presence of an organic acid, such as acetic acid and a catalytic material, such as sulfuric acid. More recently epoxidation methods have consisted of replacing the mineral acid catalyst with a sulfonated cation exchange material, such as the sulfonated copolymer of styrene divinylbenzene.

The epoxide compositions which may be used in pre-- production of these epoxides may be illustrated by the reaction of glycerol with epichlorohydrin in the presence ofboron trifluoride followed by dehydrohalogenation with sodium aluminate as follo wsz CHzOH O Fs CHOH +3CH2GHCH2C1 0 CHEOOHZCHOHCHZCl CH2OCH2CHCH2 0 CHOCHzCHOHCHzCl CHOCHzCHCHz O CHzOCHzCHOHCHzCl CH OCIHzCHClElI V It is to be-understood that such reactions do not give pure compounds and that the halohydrins formed and the epoxides derived therefrom are of somewhat varied character depending upon the particular reactants, their Other aliphatic polyepoxides useful in' proportions, reaction time and temperature. In addition to epoxide groups, the epoxide compositions may be characterized by the presence of hydroxyl groups and halogens. Dehydrohalogenation affects only those hydroxyl groups and halogenswhich are attached to adjacent carbon atoms. Some halogens may not be removed in this step in the event that the proximate carbinol group has been destroyed by reaction with an epoxide group. These halogens are relatively unreactive and are not to be considered as functional groups in the conversion of the reaction mixtures of this invention. The preparation of a large number of these mixed polyepoxides is described in the Zech patents, US. 2,538,072, 2,581,464, and 2,712,000. Still other polyepoxides which have been found to be valuable are such epoxide compositions as diepoxy butane, diglycid ether, and epoxidized polybutadiene.

Immediately following will be a description or illustration of preparations of polyepoxides which will be used in examples of compositions of this invention.

The complex resinous polyepoxides used in the examples and illustrative of the commercially prepared products of this type are the Epon resins marketed by Shell Chemical Corporation. The following table gives the properties of some Epon resins which are prepared by the condensation in the presence of alkali of bis(4- hydroxyphenyl)isopropylidene with a molar excess of epichlorohydrin in Varying amounts.

1 Based on 40% nonvolatile in butyl carbitol at 25 0.

Examples X through XII describe the preparation of typical polyepoxide polyesters.

EXAMPLE X Preparation of polyester from tetrahydrophthalic anhydride and ethylene glycol In a 3-necked flask provided with a thermometer, mechanical agitator, and a reflux condenser attached through a water trap was placed a mixture of 3 mols of tetrahydrophthalic anhydride and 2 mols of n-butanol. After melting the tetrahydrophthalic anhydride in the presence of the butanol, 2 mols of ethylene glycol were added. The reaction mixture was gradually heated with agitation to 225 C. at which point a sufficient amount of xylene was added to give refluxing at esterification temperature. The reaction mixture was then heated with continuous agitation at 225-235" C. until an acid value of 4.2 was obtained. This product gave an iodine value of 128.

Epox idation of the polyester resin In a 3-necked flask provided with a thermometer, a mechanical agitator, and a reflux condenser was placed 107 parts of the dehydrated acid form of a cation exchange resin (Dowex 50X8, 50-l00 mesh, Dow Chemical Company, a sulfonated styrene-divinylbenzene copolymer containing about 8% divinylbenzene, the percent divinylbenzene serving to control the amount of orosslinkage. The Dowex resins are discussed in publica tions entitled Ion Exchange Resins No. 1 and Ion Exchange Resins No. 2, copyright 1954 by Dow Chemical Company, the publications having form number Sp32-254 and Sp31-354, respectively) and 30 parts glacial acetic acid. The mixture of cation exchange resin and acetic acid was allowed to stand until the resin had completely taken up the acid. To this mixture was added 200 parts of the polyester resin dissolved in an equal Weight of xylene. To the continuously agitated reaction application of some external heat.

tions involving other polyester resins, .sufficient exothermic 10 mixture was added dropwise over a period of 45 minutes to 1 hour, 75 parts of 50% hydrogen peroxide. The reaction temperature was held at 60 C. requiring the (In some preparaheat is produced during the addition of hydrogen peroxide so that no external heat is required, or even some external cooling may be required.) The reaction was continued at 60 C. until a milliliter sample of the reaction mixture analyzed less than 1 milliliter of 0.1 N sodium thiosulfate in an iodometric determination of hydrogen peroxide. The product was then filtered, finally pressing the cation exchange resin filter cake. The acid value of thetotal resin solution was 42. The percent non-volatile of this solution amounting to 400 parts was 50. This 400 parts of solution wasthoroughly mixed with parts of the dehydrated basic form of Dowex 1 (an anion exchange resin of the quaternary ammonium type. Dowex l is a styrene-divinylbenzene copolymer illustrated by the formula RR N+OH where R represents the styrene-divinylbenzene matrix and R is a methyl group, manufactured by the Dow Chemical Company). The resulting mixture was then filtered followed by pressing as much of the solution as possible from the anion exchange resin cake. This product had an acid value of 4.5 and an epoxide equivalent of 288 based on a nonvolatile resin content of 42.0%. The epoxide values as discussed herein were determined by refluxing for 30 minutes a 2-gram sample with 50 milliliters of pyridine hydrochloride in excess pyridine. (The pyridine hydrochloride solution was prepared by adding 20 milliliters of concentrated HCl to a liter of pyridine.) After cooling to room temperature, the sample is then baclotitrated with standard alcoholic sodium hydroxide.

EXAMPLE XI Following the procedure of Example X a polyester resin was prepared from 5 mols of tetrahydrophthalic 'anhydride, 4 mols of diethylene glycol, and 2 mols of EYAMPLE XII The process of Example X was followed to obtain a polyester resin from 1.1 mols of tetrahydrophthalic anhydride, 1 mol, of 1,4-butanediol and 0.2 mol of nbutanol. The product had an acid value of 8.6. This polyester resin was epoxidized in the same manner to give an epoxide equivalent weight of 292 and an acid value of 5.2 on the nonvolatile content. The nonvolatile content of this resin solution was 41.9%.

Examples XIII and XIV describe the preparation of epoxidized vegetable oil acid esters.

EXAMPLE XIII Epoxidized soyabean oil acid modified alkyd resin (a) Preparation of alkyd resin-To a kettle provided with a condenser was added 290 parts of white refined soyabean oil. While bubbling a continuous stream of nitrogen through this oil the temperature was raised to 250 C., at which temperature 0.23 part of litharge was added and the temperature held at 250 C. for 5 minutes. While holding the temperature above 218 C., 68 parts of technical pentaerythritol'was added after which the temperature was raised to 238 C. and held until a mixture of 1 part of theproduct and 2 /2 parts of methyl alcohol showed no insolubility' (about 15 minutes)! At this point 136 parts of phthalic anhydridewere added and the temperature gradually raised to 25 0 C. andheld. At this point the.

condenser was removed from the kettle and the pressure reduced somewhat by attaching to a water aspirator evacuating system. With continuous agitation the mixture washeld at 250. C. until the acid value hadreached 70 partsof dehydrated acid form of a cation exchange resin (Dowex 50-X-8) and 15 parts glacial acetic acid. The mixture of cation exchange resin and acetic acid was allowed to stand until the resin had completely taken up the acid. To this mixture was added 315 parts of the alkyd resin solution described in the above paragraph and 190 parts of xylene. To the continuously agitated reaction mixture was added dropwise 38 parts of 50% hydrogen peroxide. The reaction temperature was held at 60 C. until a milliliter sample of the reaction mixture analyzed less than, one milliliter of 0.1 N sodium thiosulfate in aniodometric determination of hydrogen peroxide. The product was then filtered, finally pressing the cation exchange resin filter cake. The epoxide equivalent on the nonvolatile content was 475.

In order to remove the free acidity from the epoxidized product, 400 parts of the solution were thoroughly mixed with 110 parts of the dehydrated basic. form of Dowex 1 (an amine type anion exchange resin). The resulting mixture was then filtered, followed by pressing as much of the solution as possible from the anionexchange resin cake.

EXAMPLE XIV Epoxidized soyabean oil Admex 710, an epoxidized soyabean oil having an equivalent weight to an epoxide of 263, was dissolved in methyl ethyl ketone to a nonvolatile content. of 50%.

Admex 7 10, a product of the Archer-Daniels-Midland 12 EXAMPLE XVI In a 3.-necked. flask provided. with a thermometer, a mechanical agitator, a reflux condenser and a dropp ng funnel was plaeed 402 partsof allyl-glycidyl ether. With continuous agitation the temperature was raised. to C. at which time one part of a solution of methyl ethyl.

kctone peroxide dissolved in diethyl phthalate'to a 60%,

- content was added. The temperature was held at 160-.

Company, has an acid value of 1, a viscosity of 3.3 stokes at 25 C. and an average molecular weight of 9:37.

Examples XV and XVI describe the prepara tionof simple aliphatic polyepoxides. i i

EXAMPLE XV In a reaction vessel provided with a mechanical stirrer and external cooling means was plaeed 276 parts "of glycerol and 828 parts of. epichlorohydrin. To this reaction mixture was added 1 part of 45% boron trifluoride ether solution diluted with 9 parts of ether. The reaction mixture was agitated continuously. The temperature rose to 50 C. over a period of l hour and 45 minutes at which time external cooling with ice water was applied. The temperature was held between 50 and 75 C. for 1 hour and 20 minutes. To 370 parts of this product in a reaction vessel provided with a mechanical agitator and a reflux condenser'was added 900 parts of dioxane and 300 parts oi powdered sodium aluminate. With continuous agitation this reaction mixture was gradually heated to 92 C. over a period of 1 hour and 50 minutes, and held at this temperature for 8.hours and 50 minutes. After cooling to room temperature, the inorganic material was removed by filtration. The dioxane and low boiling products were removed by heating the filtrate to 205 C. at 20 mm. pressure to give a pale yellow product. The epoxide equivalent of this product. was determinedv by treating a l-gram sample with an excess of. pyridine containing. pyridine hydrochloride (made byaddingv 20 ccof concentrated hydrochloric acid per liter of pyridine) at the boiling point for 20- enna one epoxide group. j The epoxide equivalent on.

this product was foundztobe 152;

165? C. for a period of 8hours, adding one part of the methyl ethyl ketone peroxide solution each 5 minutes during this -hour period. After the reaction mixture had stood overnight, the volatile ingredients were removed byvacuum distillation. The distillation was started at19. mm; pressure and a pot temperature of 26 C. and volatile material finallyrernoved at a pressure of 3 mm. and a pot temperature of 50 C. The residual product had amo: lecular weight of 418, and equivalent weight to epoxide content of 198, the yield amounting to 250 parts.

The polymeric final reaction products of this invention are generally obtained by heating mixtures comprised .of

polyepoxides and mixed esiers, with or without the addition of; a catalyst, thepolymerization occurring by the application of heat. The reaction mixtures convert read ily under moderate conditions to yield the final reaction.

products, the preferred temperatures being within the range of'about 100-200 C. Whenacatalyst is employed, shorter heating periods or lower temperatures can usually be used to bring about conversion. Operable catalysts are he Friedelrcrafts yp h a orontrifluori mineral acids such as H 50 and alkaline salts such as the sodium salts of phenols or alcohols.

The reaction which takes place during the conversion of the reaction mixtures a pears complex and it is desired not to be limited by any theoretical explanation of the exact nature involved. However, it'seems likely that the reactions include polymerization of the epoxide compositions by reaction of the epoxide groups with themselves and reaction of the epoxide groups of the polyepoxides withthe active hydrogen-containing groups of the mixed esters. include the aryl hydroxyl groups contained in the 11ydroxyaryl-substituted aliphatic acid, residues of the mixed ester and aleoholic hydroxyl groups which may be present to some extent inthe mixed ester and which are formed by the splitting of epoxidegroups when the epoxide groups react with themselves or with active hydrogen-containing groups.

In preparing the new compositions, the polyepoxides and mixed esters may be used in regulated proportions without theaddition of other materials, however, other constituents such as filling and compounding materials,

7 plasticizers, pigments, etc. can be admixed with the new compositions of this invention. The method of blending would depend upon the materials and their softening point or the solubility of the material in a common solvent. For most applications it is possible to regulate proportions and types of reacting ingredients so as to obtain a product having the desired characteristics, the lack of necessity of using added plasticizers being considered one of the most important features of this invention.

The reaction mixtures and final reaction products may be prepared using varying proportions of polyepoxide and mixed ester. The quantities of reactants employed in a given instance will depend upon the characteristics desired in the final product. For example, if an alkali-sensitive coating is desired,a slight excess of acid maybe used in the mixed ester, or for certain other applications, it may be desirabie to use a large amount of polyepoxide to increase, the chemical resistance. In still other instances,- flexibility maybe increased in a, given composition by employing a mixed ester containing a relatiyely large amount of a long chain organic acid. Alternatively, flexibility may be imparted by larger amounts, of a linear long hain ep ide. In ge eral, while alarge x sso he These active hydrogen-containing compositions cific applications, most often equivalent or near equivalent ratios of polyepoxide or mixedester are employed. It has been found, therefore, that the 1:2 to 2:1 ratios give the best over-all characteristics, although ratios as 14 i good compatibility with each other, this compatibility being demonstrated by the clarity of the films prepared from the reaction mixtures. The compatibility and plasticity characteristics of these compositions can be readily adjusted by variation of the modifying acid employed in 5 high as 1:8 and 8:1 may be used. Equivalentsasexthe mixed ester. t i pressed herein refer to the weight of the polyepoxide per A further noteworthy characteristic observed in the epoxide group, in the instance of the polyepoxides, and final conversion products 18 their good adhesion to ordithe weight of the ester per hydroxyl group, in the instance nary surfaces, including metals, glass, Wood, and plastics. f th i d te l 10 The adhesive properties of the products contribute sub- The conversion of the reaction mixtures to polymeric stantially to their usefulness in the preparation of adproducts may be carried out with or without the use of hesives and coatings. The adhesive characteristics may solvents depending upon the final results desired. In the be explained by the fact that the compositions contain preparation of protective coatings, for example, it is usua high percentage of polar groups, such as ether, ester, ally desirable to apply a product dissolved ina solvent, in and alcoholic and phenolic hydroxyl groups. which case the composition will give an initial air-dry by Examples XVII through LXXXVIII, inclusive, illusmere solvent evaporation and at a subsequent time the trate the preparation of insoluble, infusible protective dried film may be converted to an infusible or insoluble coating films from the mixed esters and polyepoxides. product by the application of heat. In the preperation of In these preparations of compositions, where heat curmolding and adhesive compositions, however, it is quite ing is used to form protective coating films, each of the desirable to use a composition which contains little or no resinous mixed esters was dissolved in methyl ethyl solvent, the composition being prepared by the molten ketone or dioxane toa nonvolatile content of 40-50%. mixture of the ingredients. The polyepoxides were dissolved in methyl ethyl ketone The final reaction products of this invention possess a or xylene to a nonvolatile content of 40-60%. Mixnumber of outstanding physical properties such as hardtures of the mixed-ester solutions with the polyepoxides ness, toughness, and flexibility. In addition, these prodwere found to be stable at room temperature up to at ucts usually possess outstanding chemical properties inleast 168 hours. Mixtures of the solutions were spread eluding high resistance to oxidation, alkali and solvents. on panels with a .002 Bird applicator and the films Excellent film-forming characteristics may be obtained by baked for periods of 90 minutes at 200 C. Proproper selection of the mixed ester and the epoxide com- 30 portions hereinafter expressed refer to parts by weight position employed. In addition, mixtures may be preand are based on the nonvolatile content of the solution pared wherein the reacting ingredients generally displayed of reactants.

Films resistance Example Part of Baking No. Parts of polyepoxide mixed ester schedule,

miu./ Boiling water 5% aqueous NaOH at 25 C.

10.5 Ep0n 1001 5.0 E 10.9 Epon 1001. 5.0 1.7 5.0 12. 5.0 9.8 5.0 8.2 5.0 19. 5.0 22. 5.0 22. 5.0 is. 5. 15. 5. 20. 2. 6.3 Epon 1007 5. 22.2 Epon 1007 2. 22.2 Epon 1007 5 15013 10111007 g 5:

Films resistance Example. p Part of Baking No. Parts of polyepoxide mixed ester schedule, i

i 4 Boiling water 5% aqueous NaOH at 259 O.

XXII 1.1 Ex. 10.0 Ex. LXXIII 7.6 Ex. 10.0 Ex. 8 hrs. 30 min LXXIV 7.6 Ex. 10.0 Ex. 3hrs.

. 77.7 Ex. 10.0 Ex. 6 hrs. 30 min 6.1 Ex. 10.0 Ex. 35 min. 5.1 Ex; 10.0 Ex. 10 min. 5.1 Ex. 10.0 Ex. min. 8.7 Ex. 10.0 Ex. 10 min. 9.1 Ex. I 10.0 EX. 10 min. 1.4 Ex. 10.0 Ex. 168 hrs. 10.1 Ex. XVI. 10.0 Ex. 8 hrs. min 10.1 Ex. XVI. 10.0'Ex. min. 10.3 Ex. XVI. 10.0 Ex. 8 hrs. 30 min 7.0 Ex. XVL. 10.0 Ex. 10 min. 7.0 Ex. XVI 10.0 Ex. 15 min 8.1 Ex. XVL. 10.0 Ex. 72 hrs. LXXXVIIL 3.5m. xv 1.5 Ex. 8 hrs.

a polyhyd-ric alcoholhavinga molecular weight of not more than abo taooo and a mixture of 1) a pentanoic acid consisting essentially of 4,4 bis1(4 hydroxyvaryl)- p'eritanoic acid 'wherein'the hydroxyaryl radical is a hydroxyphenyl radical, and is free from substituents other than alkyl groups of'fromabout 1-S carbon atoms and (2) at least one aliphatic monocarboxylic acid having from bou .10.36 rbon tom an a p y p x d containing an average of more than one oxirane group per molecule whereirisaid polyepogiide is composed of the elements carbon, hydrogen and oxygen and having" oxygen. present only in the groups' selected from the group consisting of OH, COO, ethereal oxygen and oxirane groups; wherein the ratio of polyhydric alcohol to the mixture of acids of (A) is from 1:5 moles of the alcohol per mole of acid, wherein the ratio. of.

acid (1) to the acid'(2) of (A) is firoirrlzS to 5:1, and wherein 'the ratio of components (A) to (B) is from 1:8 to 8:1, all ratios being on an equivalent weight basis. i 2. The composition as described in claim 1 wherein the ratio of. polyhydric alcohol to the mixture of acids of (A) is 1:1, wherein the ratio of the acid (1) to the acid (2) of. (A) is 1:1, andwherein the ratio of cornponents (A) and (B) is from 1:2 to 2:1, all ratios being on an equivalent weight basis.

3. The composition as described in claim 2 wherein the pentanoic acid of (A) consists essentially of 4,4 (4-hydroxyaryl)pentanoic acid wherein the hydroxyaryl radical is a hydroxyphenyl radical and is free from substituents other than alkyl groups of one carbon a om. 4. The composition as describedin claim. 2 wherein the pentanoic acid of (A) is 4,4 bis(4-hydroxyphen yl) pentanoic acid.

5. The composition as describedin claim 4 wherein the modifying organic acid of (A) at least one un saturated aliphatic nionocarboxylic acid having from about 10 to 36 carbon atoms. i

Thecomposition of matter as described in claim 4 wherein (B) is a polyepoxide polyester of tetrahydrophthalic acid and a glycol wherein the epoxy oxygen bridges adjacent carbon atoms on the teirahydrophthalic idres l e 7. The composition of matter as described in claim 4 wherein (B) is an aliphatic polyepoxide, said polyepoxide having only hydroxyl substituents in addition to oxirane groups.

8. .The compositionofmatter of claim 4 wherein (B) is an epoxidized vegetable oil acid.

9. The composition of matter of claim 4 wherein (B) is an epoxidized fish oil acid.

10. The composition of claim 4 wherein the polyepoxide of (B) is a complex resinous epoxide which is a polymeric polyhydric alcohol having alternating aromatic nuclei and; aliphatic chains united through ether oxygen and terminatingii'n oxirane substituted aliphatic chains.

References Cited in the file of this patent UNITED STATES PATENTS 2,691,004 Doyle Oct. 5, 1954 

1. A NEW COMPOSITION OF MATTER COMPRISING THE CONDENSATION PRODUCT OBTAINED BY HEATING (A) AN ESTER OF A POLYHYDRIC ALCOHOL HAVING A MOLECULAR WEIGHT OF NOT MORE THAN ABOUT 8,000 AND A MIXTURE OF (1) A PENTANOIC ACID CONSISTING ESSENTIALLY OF 4,4 BIS (4-HYDROXYARYL)PENTANIOC ACID WHEREIN THE HYDROXYARYL RADICAL IS A HYDROXYPHENYL RADICAL AND IS FREE FROM SUBSTITUENTS OTHER THAN ALKYL GROUPS OF FROM ABOUT 1-5 CARBON ATOMS AND (2) AT LEAST ONE ALIPHATIC MONOCARBOXYLIC ACID HAVING FROM ABOUT 10-36 CARBON ATOMS AND (B) A POLYEPOXIDE CONTAINING AN AVERAGE OF MORE THAN ONE OXIANE GROUP PER MOLECULE WHEREIN SAID POLYEPOXIDE IS COMPOSED OF THE ELEMENTS CARBON, HYDROGEN AND OXYGEN AND HAVING OXYGEN PRESENT ONLY IN THE GROUPS SELECTED FROM THE GROUP CONSISTING OF -OH, -COO-, ETHERAL OXYGEN AND OXIRANE GROUPS; WHEREIN THE RATIO OF POLYHYDRIC ALCOHOL TO THE MIXTURE OF ACID OF (A) IS FROM 1:5 MOLES OF THE ALCOHOL PER MOLE OF ACID, WHEREIN THE RATIO OF ACID (1) TO THE ACID (2) OF (A) IS FROM 1:5 TO 5:1 AND WHEREIN THE RATIO OF COMPONENTS (A) AND (B) IS FROM 1:8 TO 8:1 ALL RATIOS BEING ON AN EQUIVALENT WEIGHT BASIS. 